5-(1-Methyl-3,4,5,6,7,7-hexachloro-norborn-4-ene-1)-isophthalic acid

ABSTRACT

New chemical compounds useful as intermediates are 5-(1-methyl3,4,5,6,7,7-hexahalo-norborn-4-ene-1)-isophthalic acid and 4-(1methyl-3,4,5,6,7,7-hexaholo-norborn-4-ene-1)-orthophthalic acid, formed by oxidation of the primary or secondary alkyl groups containing from one to ten carbon atoms on the benzene ring of the Diels-Alder adduct of equimolecular amounts of hexahalocyclopentadiene and either 3,5-dialkyl- Alpha -methylstyrene and 3,4-dialkyl- Alpha -methylstyrene. The acyl derivatives of these intermediates do not burn or support combustion and are also useful as extreme-pressure additives in lubricating oils. The following acyl derivatives of 5-(1-methyl3,4,5,6,7,7-hexachloro-norborn-4-ene-1)-isophthalic acid have been prepared: the dichloride, diamide, dianilide, diethylester, polyphenylester, poly(chlorophenyl) ester, poly-ethylene glycol ester, diphenylthioester, di-methallylester, and unsaturated polyester. Also, the co-polyphenylesters of 5-(1-methyl3,4,5,6,7,7-hexachloro-norborn-4-ene-1)- isophthalic acid and terephthalic or adipic acid; the polyamide of 5-(1-methyl3,4,5,6,7,7-hexachloro-norborn-4-ene-1)-isophthalic acid and 1,6hexanediamine; the copolyamides of 5-(1-methyl-3,4,5,6,7,7hexachloronorborn-4-ene-1) isophthalic acid and 1,6-hexanediamine and terephthalic acid or adipic acid; the co-polyethylene glycol ester of 5-(1-methyl-3,4,5,6,7,7-hexachloro-norborn-4-ene-1) isophthalic acid and terephthalic acid; and a phosphorus adduct of 5-(1-methyl-3,4,5,6,7,7- hexachloro-norborn-4-ene-1) have been prepared.

United States Patent [191 Fields et al.

[4 1 Sept. 2, 1975 5-(1-METHYL3,4,5,6,7,7-HEXACHLORO- NORBORN-4-ENE-1)-ISOPHTHALIC ACID [73] Assignee: The Standard Oil Company,

Chicago, Ill.

22 Filed: Oct. 1, 1973 21 Appl. No.: 402,486

[56] References Cited UNITED STATES PATENTS 8/1952 Herzfeld et al. 1160/3466 9/ 1960 Roberts 9/1960 Roberts 260/650 Primary ExaminerLewis Gotts Assistant ExaminerD. R. Phillips Attorney, Agent, or Firm--.lames R. l-lenes; Arthur G. Gilkes; William T. McClain [57] ABSTRACT New chemical compounds useful as intermediates are 5-( l-methyl-3,4,5,6,7,7hexahalo-norborn-4-ene-l isophthalic acid and 4-( l-methyl-3,4,5,6,7,7-hexaholonorborn-4-ene-l)-orthophthalic acid, formed by oxidation of the primary or secondary alkyl groups containing from one to ten carbon atoms on the benzene ring of the Diels-Alder adduct of equimolecular amounts of hexahalocyclopentadiene and either 3,S-dialkyl-a-methyl-styrene and methylstyrene. The acyl derivatives of these intermediates do not burn or support combustion and are also useful as extreme-pressure additives in lubricating oils. The following acyl derivatives of S-(I-methyl- 3,4,5,6,7,7-heXachloro-norborn-4-ene-l )-isophthalic acid have been prepared: the dichloride, diamide, dianilide, diethylester, polyphenylester, poly(- chlorophenyl) ester, poly-ethylene glycol ester, diphenylthioester, di-methallylester, and unsaturated polyester. Also, the co-polyphenylesters of 5-(1- methyl-3,4,5,6,7,7-hexachloro-norbom-4-ene-1 isophthalic acid and terephthalic or adipic acid; the polyamide of 5-( l-methyl-3,4,5,6,7,7-hexachloro-norborn- 4-ene-l )-isophthalic acid and 1,6-hexanediamine; the copolyamides of 5-( 1-methyl-3,4,5,6,7,7hexachloronorbom-4-ene-l) isophthalic acid and 1,6- hexanediamine and terephthalic acid or adipic acid; the co-polyethylene glycol ester of 5-(l-methyl- 3,4,5,6,7,7-hexachloro-norborn-4-ene-l isophthalic acid and terephthalic acid; and a phosphorus adduct of 5-( l-methyl-3,4,5,6,7,7- hexachloro-norborn-4-enel have been prepared. I

1 Claim, No Drawings 5 l -METHYL-3 ,4 ,5 ,6 ,7 ,7-l-IEXACI-ILORO- NORBORN-4-ENE-l )-ISOPHTHALIC ACID BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to new organic acids obtained by oxidation of the adduct of hexahalocyclopentadiene and either 3,4-dia1kyl-oz-methylstyrene or 3,5-dia1ky1-a-methylstyrene and to a method for making the same and pertains to acy] derivatives of said compounds.

2. Description of the Prior Art It is known to prepare Diels-Alder reaction products of hexahalocyclopentadiene with unsaturated organic compounds. Herzfeld et al, U.S. Pat. No. 2,606,910 (1952) reacts styrene and hexachlorocyclopentadiene to obtain the corresponding polycyclic adduct of hexachlorocyclopentadiene and styrene in a mole ratio of 1:1. Roberts, U.S. Pat. No. 2,952,71 1 (1960) makes an adduct of hexachlorocyclopentadiene and divinylbenzene by reacting approximately equimolecular proportions of hexachlorocyclopentadiene and divinylbenzene. Roberts, U.S. Pat. No. 2,952,712 (1960) makes an adduct of hexachlorocyclopentadiene and a monovinyl aromatic compound selected from the group consisting of vinyltoluene, arethylvinylbenzene, 4-tertbutylstyrene and 2,4-dichlorostyrene by reacting approximately equimolecular proportions of hexachlorocy clopentadiene and the monovinyl aromatic compound.

SUMMARY OF THE INVENTION However, it has not heretofore been known to prepare the oxidized form of the Diels-Alder reaction product of hexahalocyclopentadiene and either 3,5-dialkyl-z-methylstyrene or 3,4-dialkyl-amethylstyrene. The alkyl groups can be primary or secondary and can contain from one to ten carbon atoms. The adducts formed are 5(methyl-3,4,5,6,7,7- hexahalo-norborn-4-ene-l )-isophthalic acid and 4-(1- methyl-3,4,5,6,7,7-hexahalo-norborn-4-ene1 orthophthalic acid respectively. By our invention, these compounds are readily prepared from available and inexpensive raw materials. They are useful as intermedi ate in the production of other new and valuable derivatives. Because of their high halogen content, such new derivatives do not burn or support combustion. These .new derivatives are also useful as extreme-pressure ad ditivess in lubricating oils. For example, from the oxi dized adducts we have made esters, amides, polyesters, and polyamides, all of which are new compounds, that are useful as non-flammable plasticizers, fiberformers,

sheets, reinforced castings and moldings, pesticides,

annd 1ubricating-oil additives.

The method of formation of 5( 1-methyl-3,4,5,6,7,7- hexahalo-norborn-4-ene-1)-isophthalic acid and 4-(1- methyl-3,4,5,6,7,7-hexahalo-norborn-4ene-1 orthophthalic acid consists of two steps. The first step is adduct formation by reaction of hexahalocyclopentadiene and either 3,5-dialkyl-a-methylstyrene or 3,4-dialkyl-a-methylstyrene. The second step is oxidation of the product of the first step.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The hexahalocyclopentadiene starting material can be hexachlorocyclopentadiene or hexabrornocyclopentadiene. If the alkyl substituents on the benzene ring of the a-methylstyrene starting material are methyl groups, then the 3,5-dimethyl-a-methylstyrene or 3,4-dimethyl-a-methylstyrene can be obtained by propylation of meta-xylene or ortho-xylene, respectively, followed by dehydrogenation. The alkyl groups can be primary or secondary alkyl groups and can contain from one to ten carbon atoms.

The first step of the method of this invention consists of reacting a mixture of hexahalocyclopentadiene and either 3,5-dialkyl-a-methylstyrene or 3,4-dialkyl-amethylstyrene. The molecular ratio of the components of the mixture can range from about 1:5 to about 5:1. Preferably, equimolecular amounts of each component are used in the mixture. The components react 1:1 when the mixture is heated to a temperature in the range from C. up to 180C, for a period of time from 1 hour to 24 hours. The preferred ranges are a temperature between 135C. and 160C. and a reaction time between 3 hours and 15 hours.

The reaction pressure can be from 15 pounds per square inch to 300 pounds per square inch, and preferably 10 pounds per square inch.

The reaction is then continued by distilling the reaction mixture in vacuo at a pressure that can be in the range of from 0.1 millimeter up to 2 millimeters. The preferred range is from 0.5 millimeter up to l millimeter. The distillation is continued until the temperature of the liquid reaction mixture is from C., and preferably at least C., to 140C., but usually not over C. The adduct product crystallizes slowly. The adduct is recrystallized as white crystals from any nonpolar solvent, for example, hexane, benzene, carbon tetrachloride, toluene, or naphthalene. The recrystallized white crystals melt at 101C. More particularly, the product of step one can be represented by the product produced in accordance with the following equation:

wherein X represents a bromine or chlorine atom and R and R are primary or secondary alkyl groups containing from one to 10 carbon atoms.

The second step of the method consists of oxidizing the product of the first step. Solutions of aliphatic carboxylic acids containing two to five carbon atoms are particularly useful as the medium for such oxidation, preferably aliphatic carboxylic acids containing between two and four carbon atoms. The oxidation medium also contains salts of transition metals, preferably of cobalt, manganese, or cerium, to decompose hydroperoxides formed during the oxidation. In addition, the

oxidation medium contains a source of bromide ions, preferably ammonium bromide, sodium bromide, potassium bromide, benzyl bromide, or 1,2,2,- tribromoethane. The transition metals and bromide ions function as part of the catalyst for the reaction.

The oxidation can be effected by passing a stream of gas, preferably air, containing oxygen through the oxidation medium at a pressure from pounds per square inch to 1,000 pounds per square inch, for a period of time from onehalf hour to 10 hours. The preferred ranges are a pressure from 200 pounds per square inch to 400 pounds per square inch and a reaction time from minutes to 90 minutes. Alternatively, the oxidation can be effected using any of the other well-known chemical oxidants, for example. potassium permanganate, potassium dichromate, sodium perchlorate, manganese dioxide and dilute nitric acid. The

temperature at which the oxidation is performed can be from 100C. to 325C. The preferred range is 180C. to 250C.

The mixture of acid product and mother liquor is cooled, and the mixture is filtered to remove solid acid product. Additional acid product can be recovered from the mother liquor by distilling off -80 per cent of the mother liquor to concentrate the solution and then chilling the remaining mother liquor to a temperature between 10C. and -10C. The mother liquor is then filtered to remove solid acid product which crystallizes during chilling. The total crude acid product yield from the second step of the method is about 100 per cent.

The crude acid product is purified by dissolving it in a dilute solution of inorganic base, for example, sodium carbonate, sodium bicarbonate, or ammonium hydroxide, or organic base, including primary, secondary, or tertiary amines, for example, dimethylamine, trimethylamine or pyridine. Then the solution of acid product is treated with charcoal to remove color and filtered. The acid product is precipitated by acidifying the filtrate with an excess of an acid which is a stronger acid than the acid product, for example, dilute sulfuric acid or hydrochloric acid. The solid acid product is then filtered, washed, and dried. The acid product decomposes at 345C. without melting.

The product 5-(1-methyl-3,4,5,6,7,7-hexahalon0rborn-4-ene-l )-isophthalic acid possesses the advantage over 4-( 1-methyl-3,4,5,6,7,7-hexahalo-norborn-4- cne1 )-orthophthalic acid that its two carboxyl groups do not form an anhydride because they are in ring positions that are meta to one another. Further, the esters and amides of 5-( l-methyl-3,4,5,6,7,7-hexahalo-norborn-4-ene-l isophthalic acid are particularly thermally stable.

The following examples illustrate ways in which the principle of the invention has been applied, but are not to be construed as limiting its scope. In each example, elemental analysis was used to determine the composition of the product formed.

EXAMPLE I A mixture of 129.3 milliliters (0.8 mole) of hexachlorocyclopentadiene and 166.4 grams (0.8 Mole) of 3,5-dimethyl-oz-methylstyrene (obtained from propylation of m-xylene and dehydrogenation) was heated at 152C. for 15 hours, and then was distilled in vacuo until the temperature of the liquid was 1 10C. at 0.8 milliliters. The residue slowly crystallized and weighed 284 grams constituting an yield. It was recrystal lized from n-hexane to give white crystals, melting at 101C. of

As shown in the following tabulation, the results of elemental analysis of the product compared very closely A solution of 166 grams (0.397 mole) of the product of Example I in 1250 milliliters of acetic acid containing 33 grams of ammonium bromide, 8 grams of cobalt acetate, and 16 grams of manganese acetate was oxidized with air at 390 pounds per square inch and 400F. The cooled mixture was filtered to give a cake weighing 136 grams; 56 grams of acid product was recovered from the mother liquor. The total crude yield was percent. The acid, 5-( l-methyl-3,4,5,6,7,7-hexachloro norborn-4-ene-l )-isophthalic acid, was purified by dissolving it in 5 percent aqueous sodium bicarbonate, treating with charcoal, filtering, and acidifying with an inorganic acid like dilute sulfuric acid, dilute hydrochloric acid, or dilute nitric acid. The precipitated acid was filtered, washed, and dried. lt blackened at 345C. without melting. As shown in the following tabulation, the results of elemental analysis of the product and experimental measurement of its acid number compared very closely with the corresponding values calculated for Hi l0 -l 6 I c H Cl acid number Experimental determination 40.1 2.2 44.0 230 Calculated I values 40.2 2.1 44.4 234 EXAMPLE in A mixture of 84 grams (0.1755 mole) of l-methyl- 3,4,5,6,7,7-hexachloro-norborn-4-ene-l )-isophthalic acid and 180 milliliters (2.48 moles) of thionyl chloride, was stirred and reluxed or 96 hours, by which time all the solid had dissolved. The excess thionyl chloride, 162 milliliters was recovered by distillation at 33 40C. and 140 millimeters of pressure. The residue was crystallized from n-hexane to give 83 grams, for a 92 percent yield of 5( 1-methyl-3,4,5,6,7,7-hexachloronorborn-4-ene-1 )-isophthalic acid dichloride:

The product melted at 122C. As shown in the follow- .ing tabulation. the results of elemental analysis of the product compared very closely with the calculated elemental composition of C H O CL C H C1 Elemental analysis 372 1.6 54.9 Calculated elemental composition 37.3 1.6 55.0

EXAMPLE IV A solution of 0.516 grams (0.001 mole) of 5 (1- methyl-3,4,5,6,7,7-hexachloro-norborn-4-ene-1 isophthalic dichloride in 20 milliliters of n-hcxane was stirred with milliliters (0.1765 mole) of 30 percent aqueous ammonium hydroxide at 30C. for 10 minutes. The solid was filtered. washed, and recrystallized from ethanol to give 0.45 grams, for a 95 percent yield, of 5( 1-methyl-3,4,5.6,7,7-hexachloro-norborn-4-ene-l isophthalic acid diamide:

.The product sintered at 158C. and melted at 228C.

As shown in the following tabulation; the results of elemental analysis of the product compared very closely with the calculated elemental composition of i i i2 2 2 s C H N C 1 Experimental analysis 40.3 2.7 5.8 44.1 Calculated elemental composition 40. 3 2.5 5.9 44.6

EXAMPLE V A solution of 0.365 milliliters (.004 mole) of aniline in milliliters of benzene was added to a solution of 0.516 grams (0.001 mole) of 5-(1-methyl-3,4,5,6,7,7-

heXachloro-norborn-4-ene-1)-isophthalic acid dichlo ride in 20 milliliters of n-hexane at C. with stirring. The white solid dianilide produced was filtered, washed with benzene and water, and dried:

lt weighed 0.63 grams, for a percent yield, and after recrystallization from benzene, melted at 280C.

As shown in the following tabulation, the results of elemental analysis of the product compared very closely with the calculated elemental composition of 2a 20 2 2 s C H N Cl Experimental analysis 53.2 36 4. l 33 .4 Calculated elemental composition 53.4 3. 4.5 33.8

EXAMPLE VI A solution of 0.5l6 grams (0.00l mole) of -(1- methyl-3,4,5.6.7,7-hexachloro-norborn-4-ene-l isophthalic acid dichloride in milliliters of absolute ethanol was rcfluxed for 2 hours, and then was evaporated. The solid diethyl ester product weighed 0.53 grams, for a 100 percent yield, and was recrystallized from n-hexane:

The product melted at 101C. As shown in the follow-- ing tabulation, the results of elemental analysis of the product compared very closely with the calculated elemental composition of C H O Cl C H Cl Elemental analysis 447 3 .5 39.6 Calculated elemental composition 44.8 3.4 39.8

EXAMPLE. VII

To prepare a polyphenylester of 5( l-methyl- 3,4,5,6,7,7-hexachloro-norborn-4-ene-l )-isophthalic acid, a solution of 0.516 grams (0.001 mole) of 5-( 1 methyl-3,4,5,6,7,7-hexachloro-norbom-4-ene-l isophthalic acid dichloride in 20 milliliters of n-hexane was added with rapid stirring in a Waring blender to a solution of 0.241 grams (0.001 mole) of Bisphenol B (p,p-sec.-butylidene diphenol) in 40 milliliters of l Molar sodium hydroxide. The polyphenylester was collected on a filter, washed, and dried. The recovered product weighed 0.67 grams, or a 97 percent yield, and melted at 245C.

As shown in the following tabulation, the results of elemental analysis of the product compared very closely with the calculated elemental composition of (C H ,O Cl.;),,, where n can range from 3 to lOOJdepending on the conditions:

C H Cl Elemental analysis 57.1 2.5 30.5 Calculated elemental composition 56. l 3.5 31.1

EXAMPLE V11] To prepare a poly (chlorophenyl) ester of 5-( lmethyl-3.4.5.6,7,7-hexachloro-norborn-4-ene-l isophthalic acid. a solution of 0.516 grams (.001 mole) of 5-( l-methyl-3.4.5,6,7.7-hexachloro-norborn-4-enel )-isophthalic acid dichloride in 20 milliliters of hexane was added to a solution of 0.297 grams (0.001 mole) of dichloro Bisphenol A.

in milliliters of 1 Molar sodium hyroxide with rapid stirring in a Waring blender at 25C. The polymer was washed and dried. The product weighed 0.36 grams for a 49 percent yield. Its melting point was 286290C.

As shown in the following tabulation, the results of elemental analysis of the product compared very closely with the calculated elemental composition for 31 20 4 s To prepare a co-polyphenylester of 5-( l-methyl- 3,4,5,6,7,7-hexachloro-norborn-4-ene-l )-isophthalic acid and terephthalic acid, a solution of 0.516 grams (0.001 mole) of 5-(l-methyl-3,4,5,6,7,7-hexachloronorborn-4-ene-l )-isophthalic acid dichloride and 0.8 l32 grams (0.004 mole) of terephthaloyl chloride in 20 milliliters of benzene was added to a solution of 1.205 grams (0.005 mole) of Bisphenol B in 40 milliliters of l Molar sodium hydroxide in a Waring blender at 30C The white copolymer was filtered, washed, and

dried. The product weighed 2.05 grams for a 95 percent yield. Its melting point was 280C.

EXAMPLE X To prepare a co-polyphenyl ester of 5-( l-methyl- 3,4,5 ,6.'7,7-hexachloro-norborn-4-ene-1 )-isophthalic acid and adipic acid, a solution of 0.516 grams (0.001 mole) of 5-(1-methy1-3,4,5.6,7,7-hexachloro-norborn- 4-ene-l(-isopl1thalic acid dichloride and 0.732 grams (0.004 mole) of adipoyl chloride in 25 milliliters of nhexane was added to a solution of 1.205 grams (0.005 mole) of Bisphenol B in 40 milliliters of l Molar sodium hydroxide in a Waring blender at 30C. The white copolymer was filtered, washed and dried. The product weighed 2.0 grams for a yield of 96 percent. It melted at 178C.

EXAMPLE XI To prepare the poly( 1,6-hexane) amide of 5-(1- .methyl-3,4,5,6,7,7-hexachloro-norborn-4-ene-1 isophthalic acid, a solution of 0.516 grams (0.001 mole) 5-( 1-methyl-3,4,5,6,7,7-hexachloro-norborn-4- ene-l)-isophthalic acid dichloride in 25 milliliters of n-hexane was added to a solution of 0.12 grams (0.001 mole) of 1,6-hexanediamine in 40 milliliters of 1 Molar sodium hydroxide in a Waring blender. The polyamide was filtered, washed, and dried. The product weighed 0.17 grams for a yield of 48 percent. Upon heating, the product darkened at 280C. and melted at 308C. As shown in the following tabulation, the results of elemental analysis of the product compared very closely with the calculated elemental composition of (C H O Cl N where m can be 3 to 100 depending on the conditions used;

C H C1 N Elemental analysis 46.8 4.2 37.7 5.4 Calculated elemental composition 47.3 3.9 38.1 5.0

EXAMPLE XII To prepare a copolyamide of S-(l-methyl- To prepare a copolyamide of S-(I-methyl- 3,4,5,6,7,7-hexachloro-norborn-4-ene-l )-isophthalic acid and adipic acid, a solution of 0.516 grams (0.001 mole) of 5 -(l -methyl-3 ,4 ,5 ,6 ,7 ,7-hexachloro-norborn- 4-ene-1 )-isophtha1ic acid dichloride and 0.732 grams (0.004 mole) of adipoyl chloride in 25 milliliters of nhexane was added at 25C. to 0.6 grams (0.005 mole) of 1,6-hexanediamine in 40 milliliters of 1 Molar sodium hydroxide in a Waring blender. The copolyamide was filtered, washed, and dried. The product weighed 1.36 grams for a 92 percent yield and melted at 255C.

EXAMPLE XIV To prepare the poly-ethylene glycol ester of 5-(1- methyl-3,4,5,6,7,7-hexachloro-norbom-4-ene-l isophthalic acid, a mixture of 0.516 grams (0.001 mole) of 5-( l-methyl-3,4,5,6,7,7-hexachloro-norborn- 4-ene-l )-isophthalic acid dichloride and 10 milliliters of a solution of 0.62 grams (0.01 mole) of ethylene glycol in 100 milliliters of 1,2 -dimethoxy ethane containing 0.001 mole of ethylene glycol was refluxed under dry nitrogen for 4 hours, then evaporated in a stream of dry nitrogen and heating continued for 3 hours at 150C. The polymer weighed 0.482 grams for a 95 percent yield and melted at 266-267C. As shown in the following tabulation, the results of elemental analysis of product compared very closely with the calculated elemental composition of (C I-l O C1 where m can be 3 to depending on the conditions used:

C H Cl Elemental analysis 42.6 2.7 41.5 Calculated elemental composition 42.8 2.4 42. 1

EXAMPLE XV EXAMPLE XVI To prepare the di-phenylthioester of 5-( l-methyl- 3 ,4 ,5 ,6 ,7 ,7-hexachloro-norborn-4-ene-l )-isophtha1ic acid, a solution of 2.068 grams (0.004 mole) of 5-(1- methyl3,4,5,6,7,7-hexachloro-norborn-4-ene-l isophthalic dichloride in 5.5 grams (0.05 mole) of benzenethiol was heated at C. for 4 hours, then evaporated on the steam bath. The product 1 1 weighed 3.4 grams for a yield of 98 percent and melted at 196C. after crystallization from ethanol.

EXAMPLE XVII To prepare the di-methallyl ester of -(1-methyl- 3,4,5 ,6,7,7-hexachloro-norborn-4-ene-l )-isophthalic acid, a solution of 5.61 grams (0.01 mole) of 5-(1- methyl-3,4,5,6,7,7-hexachloro-norborn-4-ene-1 isophthalic dichloride in 7.2 grams (0.01 mole) of methallyl alcohol was refluxed with 8 milliliters (0.01 mole) of pyridine for 10 minutes. The cooled mixture was poured into water; the heavy layer was extracted with 50 milliliters of carbon tetrachloride, washed, dried, and evaporated on the steam bath, giving 6.2 grams, or a 98 percent yield of light yellow, viscous di-methallyl EXAMPLE xx The products of Examples I through XIX did not burn or support combustion; even the copolymers of 5 Examples IX, X, XII, XIII, and XV were selfextinguishing.

A mixture of 2 grams of the unsaturated polyester formed in Example XIX and 2 grams of styrene was warmed at 80C. to effect solution, then heated with 10 0.01 grams of benzoyl peroxide at 100110C. for 2 hours to give a clear, hard resin that did not burn.

EXAMPLE XXI ester. 15 Mixed polyesters are prepared from ethylene glycol i 3 c m .-c :en

' CH1; C J

0 CH C CH As shown in the following tabulation, the results of eleand terephthalic acid with 5-( 1-methy1-3,4,5,6,7,7- mental analysis of the product compared very closely hexachloro-norborn-4-ene-l )-isophthalic acid dichlowith the calculated elemental composition of ride. The acid and the acid dichloride are mixed in pro- 2 22 4 n portions in the ranges of from 10 percent up to 75 percent terephthalic acid, from 25 percent up to 90 percent 5-( l-methyl-3,4,5,6,7,7-hexachloro-norborn-4- C H ene-1)-isophthalic acid dichloride. The molar ratio of Elemental analysis 4346 18 330 ethylene glycol to the mixture of the acid and acid dig t f elemental chloride is 1:1. The reactions proceeds by a condensa- Ompos tion well known in the art. The polyesters thus prepared do not burn or support combustion.

A 0.5 gram sample of this ester, heated with 0.01 40 EXAMPLE X rams ob benzo l eroxide at 100C. f 70 h i brittle, yellowyreiin or ours gave Mixed polyamides are prepared from the 1,6- hexanediamine and adipic acid with 5-( l-methyl- EXAMPLE XVIII 3,4,5,6,7,7-hexachloro-norborn-4-ene-l )-isophthalic To prepare a phosphorus derivative of 5-(1-methylf dlchl9ndel acld and gi chloride are mlxed 3,4,5,6,7,7-hexachloro-norborn-4-ene-1)-isophthalic m z g t e i 0 mm 10 percent up to acid, a solution of 4.5 grams (0.0072 mole) of the di- 80 percent exanedlamme from 20 percent up to methallyl ester of Example XVII inn 20 milliliters of 90 percmt h & 7 toluene was stirred and refluxed for 4 hours with 1.506 norlwn'li'enc'l )qsopihthallc ,acld dlchlonde The grams (0.0072 mole) of phosphorus pentasulfide. The T 93 ratio 2 i g ig q fi ig the nilxture of cooled mixture was filtered and evaporated, giving 5 a an z ig: profee S grams of reddish, very viscous phosphorous adduct. L ensa 3 i g m t e e E i The results of elemental analysis are 26.4% P and 9.5% 1 es t us prepare 0 not um or Support com usnon' S 5 EXAMPLE XXIII EXAMPLE XIX An unsaturated polyester of 5-( 1-methyl-3,4,5,6,7,7- hexachloro-norborn-4-ene-1 )-isophthalic acid was prepared by heating a mixture of 2.14 grams (0.004 mole) of the diethyl ester of 5-( l-methyl-3,4,5,6,7,7- hexachloro-norborn-4-ene-l)-isophthalic acid, the product of Example VI, 1.24 grams (0.02 mole) of ethylene glycol, and 1.56 grams (0.016 mole) of maleic' anhydride at l50l 80C. under dry nitrogen for 3 hours. Heating was continued at 185C. under 100 milliliters of pressure for 2 hours, giving 4.5 grams for a 99 percent yield of clear, very viscous polyester.

The products of Examples XVII and XVIII were tested as extreme-pressure additives in SW oil on the Almen machine (which is described in Almen, U.S. Pat. No. 2,001,861 (1935)), with these results:

Additive Pass. lbs. Fail, lbs.

0 4 6 1% Example l7 l6 18 171 Example 18 30+ The products of this invention can be used in oils at hexachloro-norborn-4-ene-l )-isophthalic acid, of the Concentrations of 0.001 to percent by weight. Diels-Alder adduct of equimoiecular amount of hexa- What is claimed is: chioro cyclopent adiene and 3,5-dialkyl-aiphal. The oxidation product, 5-(1-methy1-3,4,5,6,7.7- methylstyrene.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,903,144

DATED I Sept. 2, 1975 INVENTOMS) 1 Ellis K. Fields and Alfred Steitz, J r.

Q It is certified that error appears m the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 38, "5-(methyl-3,4,5,6,7,7-" should be 5-(l-methyl-3,4,5,6,7,7-

' 5, l2, "reluxed'or" should be refluxed for Signed and Scaled this twenty-fifth D a Of November 19 75 ISEAL] Attest:

RUTH. C. HSON C. MARSHALL DANN A N" 011166 (mnmissinner ufPatems and Trademarks 

1. THE OXIDATION PRODUCT, 5-(1-METHYL-3,4,5,6,7,7-HEXACHLORO-NORBORN-4-ENE-1)-ISOPHTHALIC ACID, OF THE DIELS-ALDER ADDUCT OF EQUIMOLECULAR AMOUNT OF HEXACHLORO CYCLOPENTADIENE AND 3,5-DIALKYL-ALPHA-METHYLSTYRENE. 